4-Bromo­seleno­anisole

Sørensen, H.O.; Stuhr-Hansen, N.

doi:10.1107/S160053680902296X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages o1665-o1666

doi:10.1107/S160053680902296X

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4-Bromoselenoanisole

Henning Osholm Sørensen ^a ^* and Nicolai Stuhr-Hansen ^b

^aCenter for Fundamental Research: Metal Structures in Four Dimensions, Risø National Laboratory for Sustainable Energy, Technical University of Denmark, Frederiksborgvej 399, P.O. 49, DK-4000 Roskilde, Denmark, and ^bDepartment of Medicinal Chemistry, University of Copenhagen, Universitetsparken 2, DK-2100 Copenhagen, Denmark
^*Correspondence e-mail: osho@risoe.dtu.dk

(Received 10 June 2009; accepted 15 June 2009; online 24 June 2009)

The title compound, 1-bromo-4-methylselenobenzene, C₇H₇BrSe, was prepared by methylation of 4-bromoselenophenolate with methyl iodide, and crystals suitable for structure determination were obtained by sublimation. The molecule is essentially planar; the Se—Me bond is rotated by only 2.59 (19)° out of the least-squares plane of the benzene ring. The most pronounced intermolecular interactions are two hydrogen bonds of the type C—H⋯π, which determine a herring-bone pattern in the crystal packing.

Related literature

For related selenobenzene structures, see: Oddershede et al. (2003 ); Sørensen & Stuhr-Hansen (2009 ); Stuhr-Hansen et al. (2009 ). For the ⁷⁷Se-NMR spctrum, see: Eggert et al. (1986 ). For the melting point, see: Gilow et al. (1968 ).

Experimental

Crystal data

C₇H₇BrSe
M_r = 250.00
Orthorhombic, P n a 2₁
a = 5.8298 (8) Å
b = 7.0671 (11) Å
c = 18.776 (6) Å
V = 773.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 11.86 mm⁻¹
T = 122 K
0.36 × 0.09 × 0.09 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: numerical (DeTitta, 1985 ) T_min = 0.145, T_max = 0.454
5823 measured reflections
1590 independent reflections
1590 reflections with I > 2σ(I)
R_int = 0.031
5 standard reflections frequency: 166.7 min intensity decay: 8.7%

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.075
S = 1.15
1590 reflections
83 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −1.30 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: −0.01 (4)

Table 1
Selected bond lengths (Å)

Se1—C1	1.916 (4)
Se1—C7	1.930 (5)
Br1—C4	1.906 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯C2ⁱ	0.95	2.84	3.747 (4)	159
C5—H5⋯C5ⁱⁱ	0.95	2.83	3.740 (5)	160
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: DREAR (Blessing, 1987 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902296X/fj2225sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902296X/fj2225Isup2.hkl

checkCIF report

Related literature top

For related seleno-benzene structures, see: Oddershede et al. (2003); Sørensen & Stuhr-Hansen (2009); Stuhr-Hansen et al. (2009). For the 77Se-NMR spctrum, see: Eggert et al. (1986). For the melting point, see: Gilow et al. (1968).

Experimental top

The title compound was synthesized as described below. To a stirred solution containing di(4-bromophenyl) diselenide (2.35 g, 5 mmol) and hydrazine hydrate (2.75 mmol) in DMSO (8 ml) was added 25% methanolic sodium methanolate (approximately 2 g, the last 0.2 g added dropwise with intervals of 5 s until the yellow color of di(4-bromophenyl) diselenide disappeared). 4-Methyliodide (1.70 g, 12 mmol) was added and the reaction mixture was further stirred for 10 minutes. The clear colourless reaction mixture was diluted with water (100 ml) and extracted with ether (3 x 25 ml). The combined organic phases were washed with water (15 ml), filtered through alumina (neutral, 6 g) by means of pentane and the solvent was evaporated in vacuo. Sublimation (200 °C, 5 m mH g) gave the title compound 4-bromoselenoanisol (2.24 g, 90%) as long white needles in a quality suitable for structure determination by single-crystal x-ray diffraction; mp 47–48 °C (lit. (Gilow et al., 1968) mp 46–47 °C). C₇H₇BrSe: found C 33.69% H 2.57%; calc. C 33.63% H 2.82%. Mass spectrum (EI; m/z, relative intensity): 250 (M⁺, 100), 235 (67), 171 (7), 156 (56). ¹H-NMR (CDCl₃) δ: 2.33 (3H, s), 7.26 (2H, d, J = 8.6 Hz), 7.36 (2H, d, J = 8.6 Hz). 77Se-NMR (Eggert et al., 1986) (CDCl₃) δ: 211 p.p.m..

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: DREAR (Blessing, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Ortep drawing (Johnson, 1976) of the title compound including labelling of the atoms. The displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres with an arbitrary radii.

1-bromo-4-methylselenobenzene top

Crystal data top

C₇H₇BrSe	F(000) = 472
M_r = 250.00	D_x = 2.147 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2c -2n	Cell parameters from 20 reflections
a = 5.8298 (8) Å	θ = 39.2–40.3°
b = 7.0671 (11) Å	µ = 11.86 mm⁻¹
c = 18.776 (6) Å	T = 122 K
V = 773.6 (3) Å³	Needle, white
Z = 4	0.36 × 0.09 × 0.09 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1590 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 74.8°, θ_min = 4.7°
ω–2θ scans	h = −7→7
Absorption correction: numerical (DeTitta, 1985)	k = −8→8
T_min = 0.145, T_max = 0.454	l = −23→23
5823 measured reflections	5 standard reflections every 166.7 min
1590 independent reflections	intensity decay: 8.7%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0537P)² + 0.4964P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.075	(Δ/σ)_max < 0.001
S = 1.15	Δρ_max = 0.62 e Å⁻³
1590 reflections	Δρ_min = −1.30 e Å⁻³
83 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0128 (5)
Primary atom site location: heavy-atom method	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (4)

Crystal data top

C₇H₇BrSe	V = 773.6 (3) Å³
M_r = 250.00	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 5.8298 (8) Å	µ = 11.86 mm⁻¹
b = 7.0671 (11) Å	T = 122 K
c = 18.776 (6) Å	0.36 × 0.09 × 0.09 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1590 reflections with I > 2σ(I)
Absorption correction: numerical (DeTitta, 1985)	R_int = 0.031
T_min = 0.145, T_max = 0.454	5 standard reflections every 166.7 min
5823 measured reflections	intensity decay: 8.7%
1590 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.075	Δρ_max = 0.62 e Å⁻³
S = 1.15	Δρ_min = −1.30 e Å⁻³
1590 reflections	Absolute structure: Flack (1983)
83 parameters	Absolute structure parameter: −0.01 (4)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Se1	−0.08215 (7)	0.05711 (4)	0.00008 (2)	0.02110 (15)
Br1	0.38155 (8)	−0.04502 (5)	0.317143 (19)	0.02756 (16)
C1	0.0636 (7)	0.0211 (5)	0.0905 (2)	0.0176 (7)
C2	−0.0585 (6)	0.0834 (5)	0.1507 (2)	0.0185 (7)
H2	−0.2055	0.1395	0.1450	0.022*
C3	0.0336 (8)	0.0636 (4)	0.2178 (2)	0.0219 (8)
H3	−0.0478	0.1066	0.2586	0.026*
C4	0.2483 (6)	−0.0207 (5)	0.22490 (18)	0.0184 (7)
C5	0.3691 (6)	−0.0843 (5)	0.1666 (2)	0.0184 (7)
H5	0.5149	−0.1420	0.1727	0.022*
C6	0.2759 (7)	−0.0633 (4)	0.0982 (2)	0.0193 (8)
H6	0.3579	−0.1067	0.0577	0.023*
C7	0.1556 (9)	−0.0397 (6)	−0.0615 (3)	0.0300 (9)
H7A	0.2997	0.0268	−0.0517	0.045*
H7B	0.1117	−0.0195	−0.1113	0.045*
H7C	0.1759	−0.1753	−0.0528	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0191 (2)	0.0252 (2)	0.0190 (2)	0.00090 (10)	−0.00294 (17)	0.00115 (15)
Br1	0.0276 (2)	0.0363 (3)	0.0188 (2)	0.00065 (13)	−0.00506 (19)	0.00065 (16)
C1	0.0174 (18)	0.0161 (14)	0.0193 (18)	−0.0014 (12)	−0.0005 (13)	0.0019 (13)
C2	0.0120 (15)	0.0178 (15)	0.026 (2)	0.0030 (12)	0.0026 (13)	−0.0003 (13)
C3	0.022 (2)	0.0201 (16)	0.024 (2)	0.0001 (11)	0.0034 (17)	−0.0019 (12)
C4	0.0186 (19)	0.0202 (16)	0.0166 (17)	−0.0032 (12)	−0.0007 (15)	0.0015 (12)
C5	0.0168 (15)	0.0206 (14)	0.0177 (18)	−0.0018 (12)	0.0009 (13)	−0.0014 (13)
C6	0.0170 (19)	0.0178 (16)	0.0230 (19)	0.0009 (10)	0.0012 (16)	−0.0022 (11)
C7	0.032 (2)	0.039 (2)	0.019 (2)	0.0061 (15)	0.0035 (18)	−0.0038 (14)

Geometric parameters (Å, º) top

Se1—C1	1.916 (4)	C3—H3	0.9500
Se1—C7	1.930 (5)	C4—C5	1.377 (5)
Br1—C4	1.906 (4)	C5—C6	1.401 (6)
C1—C6	1.382 (5)	C5—H5	0.9500
C1—C2	1.406 (5)	C6—H6	0.9500
C2—C3	1.377 (6)	C7—H7A	0.9800
C2—H2	0.9500	C7—H7B	0.9800
C3—C4	1.392 (6)	C7—H7C	0.9800

C1—Se1—C7	99.5 (2)	C4—C5—C6	119.7 (3)
C6—C1—C2	120.3 (4)	C4—C5—H5	120.2
C6—C1—Se1	123.2 (3)	C6—C5—H5	120.2
C2—C1—Se1	116.5 (3)	C1—C6—C5	119.3 (4)
C3—C2—C1	120.4 (4)	C1—C6—H6	120.4
C3—C2—H2	119.8	C5—C6—H6	120.4
C1—C2—H2	119.8	Se1—C7—H7A	109.5
C2—C3—C4	118.8 (4)	Se1—C7—H7B	109.5
C2—C3—H3	120.6	H7A—C7—H7B	109.5
C4—C3—H3	120.6	Se1—C7—H7C	109.5
C5—C4—C3	121.6 (3)	H7A—C7—H7C	109.5
C5—C4—Br1	119.0 (3)	H7B—C7—H7C	109.5
C3—C4—Br1	119.5 (3)

C7—Se1—C1—C6	−3.0 (3)	C2—C3—C4—Br1	178.8 (3)
C7—Se1—C1—C2	177.8 (3)	C3—C4—C5—C6	0.4 (6)
C6—C1—C2—C3	1.0 (5)	Br1—C4—C5—C6	−178.5 (3)
Se1—C1—C2—C3	−179.8 (3)	C2—C1—C6—C5	−0.7 (5)
C1—C2—C3—C4	−0.6 (5)	Se1—C1—C6—C5	−179.8 (3)
C2—C3—C4—C5	−0.1 (5)	C4—C5—C6—C1	0.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···C2ⁱ	0.95	2.84	3.747 (4)	159
C5—H5···C5ⁱⁱ	0.95	2.83	3.740 (5)	160

Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x+1/2, −y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₇H₇BrSe
M_r	250.00
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	122
a, b, c (Å)	5.8298 (8), 7.0671 (11), 18.776 (6)
V (Å³)	773.6 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	11.86
Crystal size (mm)	0.36 × 0.09 × 0.09

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Numerical (DeTitta, 1985)
T_min, T_max	0.145, 0.454
No. of measured, independent and observed [I > 2σ(I)] reflections	5823, 1590, 1590
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.075, 1.15
No. of reflections	1590
No. of parameters	83
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −1.30
Absolute structure	Flack (1983)
Absolute structure parameter	−0.01 (4)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), DREAR (Blessing, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Se1—C1	1.916 (4)	Br1—C4	1.906 (4)
Se1—C7	1.930 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···C2ⁱ	0.95	2.84	3.747 (4)	159.4
C5—H5···C5ⁱⁱ	0.95	2.83	3.740 (5)	160.3

Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x+1/2, −y−1/2, z.

Acknowledgements

The authors wish to thank Flemming Hansen, Centre for Crystallographic Studies, University of Copenhagen for obtaining the crystallographic data. HOS acknowledge support from the EU Sixth Framework Programme TotalCryst and the Danish National Research Foundation.

References

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